Process of making ammonium chloride



Jan. 8, 1935. s. B. HEATH I PROCESS OF MAKING AMMONIUM CHLORIDE Filed July 3, 1933 INVENTOR Jkaldan B. Healh BYMW M 56: M

ATTORNEYS Patented Jan. 8, 1935 Emqcsss 6F MAKiim 1M 1 V 1 Sheldon rliFHeath,oMidlandfiiMich :assighb'md. is lflihe Dow flhemical Comgany, lylidland Mjohap; I

I eorporation ofMichigan I I W I W mplicat ng-Julya; 933;"seriai' Novt1s;s03 r I recla s. V (01 23-100) This. invention is with the 'clirect reaction ofrsub'stantialiyfiry ammonia and'hy drogenhhleride in vaporphase, to produce am mohiumchloride. .Theladva'ntage of this general .5 method .of. preparation fas'i w'e11' known, is in the-avoidance of handling aqueous solutions;,,from

whichon aceounteofbitheir-l.orrosiveness to metals, 'it is extremelydiflieult to crystallize a product free'frommetallieimpurities. J. I llThere are wllknownidiffieulties; howeveniconnectedoiit .the reaotioniin the vaporbinhase. 'iForlexamble, it leadsltd thejforma tion. of.a ffog .consi 'sting,of impalpi ble particles whiehllfloat air..a .rid settle .veiy s1w1y, On ac count-of lthe\-excessii ely 'slow raterofiproduclti onflin'tnroportionjto.the volume of reaction space wfiiehgisobtaind by this method, at moderate mg-fies temperatures, it has been'propo'sed to .inereaselthe rate of .oi tput IbyTincr'ea'sing so .the reaction: temperature; e.;g; no aboi fifi oof'rC, so that'the product is'formedas afiibrous crystalline mass like .sublimecl sal ammoniac. This change still does not; permit. of a very gjreat iincrease"in routputlhowever; arid 'thesolid cake, prdducjedjis .not desirable for 'manmndustrm usesoffa'mmonium chloride. I'Moreover,"the'reaCtiOmQ Q mOt 'be Lcarrid .oiit at "the required temperature in apparatuslhaving' metalllicflsurfaces exposed to the reactio'ni materials. j :lhave .nowifoundthattherate of reacti'on may be vyery greatly in'oreased with only ajmo'derate .inereasesof temperature. above normal 'by prospeeding inthelfollowing,fdescribedimanner. :Ac-

cording to my improvedgrprocedure the" reacting -35 materials, ammonia andlhydrog'en chloride, are introduced'in proper combining "pro jortions into "a rapidly flowing current er a=gasyeither a; substantiaglly'n n reaBtiVeEgas; such as air; nitrogen, "etc.',' or an'exeess "of one of thereactaints whieh gas 'current jis'constantly reC'ycIedE D-he partibles of ammonium Chloridaiheld insuspension' in the gas murrent while 'the'y 'grow i in size 1 until large enough to settl'e qfiicklyzby theirrownzweight i when theirimotion'x isarrested'byt causing? them to irimpmge upon'r a surface of thenapparatusmhich is interposed in their path. In this wayr theprod- --u'ot is-obta-ineddn .theriorm: ofrfinegrained particles more or Jess -spherical. shape. and quite uniform. flhet-im-proved process can rhe -carried. out, 1at the temperaturesvempioyed, in apparatus constr-ucted ofracorrosion resistantmetal; orof =onewhosechloride ishsubstaltntially non-volatile :at the reaction temperature without .introdue,- ing metallic impurities into, or discoloring, the 5 mroduct; *Th i rol qwmsf esqrip qn {sets forth in detail I whieh, is e'xpla ined 'withj rfereneej to the annexed (d ag wi a,

glii said "'zlrajwing ,fthe single'f figtire' represents a form Elf/apparatus suitable. foricarrying out; the

invention; "abemrifueal, Ia '1- or usual, type,

having a'igajs inlet "2," andfoiitl'et .13; is; connected in [closed circuit .with a "duetfsystem consisting of Vertical m mbersr and 5,19; U "oonneetor (j and a? return (duct? '7 {member 4 "being ,directly ponheated. to' Outlet ;3'andret1irn ufotfl'ito inlet'2 'of th" l'fan' 1., .In.memBer "4. gr valve-controlled iifltsi iafid' ammfii ai an 'fh ro ridej respectively,lbeingipreferably inserted at an ang e as show In* the:b,ott'om of. .the horizontal Po tion f r u k v preierably ofismaller diameter thanfduetfi." outlei-10f jeomjmimi'catesjiwith; aiclosed -receiver -11 bef'made adjustable'fhy'bein g piir'ote'dpreferably l'et 10. suitablefgau'ges andfmea'sl ringiinstrue ments for determjiningthe temperature, :velocity,

La s'peedjto' maintain a siiffiQi ent" air velocity mine: duct systemfyvhichinpractiee is 'variedibetjween about 200Q-arid5000 feet or" more :per mi ute: although thesefig ires are n mo be regarded asflimitingthe invention, ,The Ciroi1lating',gases are heateclby'the heat of reaction, 'but the 'temperature'jismaintained between about s "v and, about 200 .q. by regulating"? the rate'of introducing the ammoniafandfhydrogen chloride.

By prdviding. Iorflrabid Jrafdiation -of heat from To start the proeess the ia n is set in motion,

ehlorid'ej is charged intofthe' sy'stemwh'ereit is siisiir'idedfin. the] ,air"current. Ammonia and hydrogen v.elileride .ar'e ltlfiengadmitted in" about lpombininig gl propoitions *aifid freactl promptly to formed. As the formation of ammonium chloride 7 and the growth (of the} particles continues, the loading of theair current increases to the point where the heavier particles commence to settle out and are discharged through outlet 10. The separation of the particles isassisted by .the. deflector 14, against which some of the suspended particles constantly strike and are caused 'to settle out by the sudden stoppage of their motion.

Deflector 14 may be adjus'tedat various angles to control the deposition of the heavier particles,

of the particles discharged.

By maintaining the temperature in the system at a point below that at which ammonium chloride has a-material vapor pressure, the sublimation of the product and formation of a solid coating ofsublimed material on the duct surfaces is largely avoided, as already indicated, temperatures'below about 200 ,CQbeing satisfactory. An additional aid to the prevention of'caking in the pipes, I have found, is the scouring or eroding action of the granular ammonium chloride particles whichpare carried by the recirculating gas current. These particles, due to their rapid motion, act similarly to a. sandblast to keep the duct surfaces scoured clean, while the hardness of the particlesis not sufficient to cause erosion of the metal -itself.. Theadditionpfga small amount of solid ammonium chloride particles in starting operation. of the process, as aforementioned, isinstrumental in keeping the metal, surfaces scoured until thenewly formed particles are built .up to a large enough size to continue this action.

As a practical example of the 'workingof my improved process, a ductv system'was" employed composed of 8 inch diameter pipe made" of a magnesium-manganese alloy containing 1.5 per cent of manganese, the total length of piping being 18 feet. The fan was operated at a speed to maintain a gas velocity of about 4800 feet per minute in the System, and ammonia andhydrogen-chloride were admitted at a rate to produce from 16 to 21 pounds of ammonium chloride per hour. fAt this operating rate the temperature varied. from about to about C. The product, which settled out in the form of small shot having a size up to about inch, was white in color, free from heavy metal impuritiesand contained 99.7 per cent NH4C1.

In the foregoing examplejthe reacting gases were nearly anhydrous, the ammonia .being substantially 100 percent pure, while the hydrogen chloride was about 80 percent pure, being diluted with air. It is desirable to employ nearly dry gases, althougha trace of water seems to be necessaryto catalyzethe reaction. Since some air is continuously vented from the system, it is feasible to employ. gases containing an appreciable amount of water vapor, the excess water vapor being vented from the system with the air, while the reaction temperature is maintained at a point to prevent condensation of moisture."

When it is desired to carry out the process under conditions where stron hydrogen chloride gas is not readily available, the hereinbefore described procedure may be modified to permit the use of chlorine instead of hydrogen chloride. "Chlorine reacts with ammonia'to form hydrogen chloride, according to the equation; (1) 3C12+2NH36HC1+Nz Equation (2), a mixture of hydrogen chloride and,.am1n0nium, .ch10ride is formed. Small amounts'of'riitrogen chloride or chloramines, which discolor the ammonium chloride product,

may also be formed inside reactions, unless the temperature' is raised to about 300 C. At such temperatures the'ammonium chloride is largely thereby affording a degree of-control of thesize dissociatedintohydrogen chloride and ammonia, which recombine upon cooling. A temperature as high'as 300 C., or thereabout, is not suitable for the process of this invention, as it would preventiseparation of solid particles in the manner already described and also subjectthe metallic parts of the apparatus to attack. In order to adapt the usev of chlorine, instead of hydrogen chloride, as primary raw material in my process, I maylreact chlorine withless ammonia than corresponds to Equation 2);fat about 300C. in a separate reactor'not' shown in the drawing, and then introduce the hot. gaseous mixture of ammonium chloride, hydrogen chloride and nitrogen through inlet pipe" 9 into the apparatua'where itiinter'mixes with cold ammonia introduced through inlet 8, asiwell as with'the recirculated gases, to lower the temperature of the combined gases to a point below 200 C. Thence the operation proceeds inithe manner already described, the excess nitrogen formed inthe reaction of chlorine and ammonia .being vented'at l2,

" Theapparatus employed in my improved b i cess',such as fan, pipes, etc. may be made of any corrosion-resistant metaL or of one: whose chloride'has no appreciable vapor pressure at the reactionftemperature. Ordinary iron and alu minum are undesirable, sincet he respective M chlorides are sufliciently volatile to carry over metallic impurity into the. ammonium f chloride product. I have found magnesium, or magnesium base alloys, especially suitable, for the purpose,

this metal. Howeveniother' metals resistant to at,- tack, such as high chromium irons, nickel, nichrome, etc. maybe employed, as well as other resistant materials, such as enameled iron or ceramictile and the like.

Other. [ammonium jhalides, particularly animoniumfbromide, may also be made by reacti'ng gaseous ammonia and hydrogen bromide in accordance with the hereinbefore described process.

Othermodes of applying the principle of my invention may beemployed instead of the one explained, change beingmadeas regards the process herein disclosed, provided the step or steps stated by any of theifollowing claims or the equivalent of such stated step-or steps be employed. 7

I therefore particularly point out and distinctly claim as my inventiona- .and prefer to use apparatus constructed from V 1 Process of making ammonium chloride which I comprises the stepof reacting gaseous ammonia comprises rapidly circulating in a closed system a gaseous current containing small granular particles of ammonium chloride suspended therein and adding ammonia and hydrogen chloride to the current.

3. Process as claimed in claim 2, in which the supply of hydrogen chloride is intermixed with ammonium chloride previously formed by reaction of ammonia and chlorine.

4. Process of making ammonium chloride which comprises rapidly circulating in a closed system a non-reactive gaseous current containing small granular ammonium chloride particles suspended therein, adding ammonia and hydrogen chloride in approximately combining proportions at a rate such as to maintain the temperature of the system between about and 200 C. and continuously removing a portion of the ammonium chloride particles from said current.

5. Process of making ammonium chloride which comprises reacting gaseous ammonia and hydrogen chloride in a rapidly flowing current of a non-reactive gas containing small granular particles of ammonium chloride suspended therein, continuously recirculating the gases while additional particles are formed therein, arresting the motion of a portion of the suspended particles to cause the same to settle out and removing the separated particles.

6. In a process of making ammonium chloride by reacting gaseous ammonia and hydrogen chloride in a rapidly flowing current of a nonreactive gas at a temperature below about 200 0.,

the improvement which consists in carrying out the process in contact with surfaces of magnesium or a magnesium base alloy.

7. Process of making an ammonium halide which comprises rapidly circulating in a closed system a non-reactive gaseous current containing small granular particles of the halide suspended therein and adding ammonia and the correspond- 7 ing hydrogen halide to the current.

8. Process of making ammonium bromide which comprises rapidly circulating in a closed system a non-reactive gaseous current containing small granular particles of the bromide suspended therein and adding ammonia and hydrogen bromide to the current.

9. Process of making ammonium bromide which.

SHELDON B. HEATH. 

